EP3055453A1 - Matériaux à base de lignocellulose contenant de la cellulose défibrillée - Google Patents

Matériaux à base de lignocellulose contenant de la cellulose défibrillée

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Publication number
EP3055453A1
EP3055453A1 EP14777094.5A EP14777094A EP3055453A1 EP 3055453 A1 EP3055453 A1 EP 3055453A1 EP 14777094 A EP14777094 A EP 14777094A EP 3055453 A1 EP3055453 A1 EP 3055453A1
Authority
EP
European Patent Office
Prior art keywords
lignocellulose
wood
mixtures
microfibrillated cellulose
materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14777094.5A
Other languages
German (de)
English (en)
Other versions
EP3055453B1 (fr
EP3055453C0 (fr
Inventor
Matthias Schade
Stephan WEINKÖTZ
Jens Assmann
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BASF SE
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BASF SE
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Publication of EP3055453B1 publication Critical patent/EP3055453B1/fr
Publication of EP3055453C0 publication Critical patent/EP3055453C0/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • B29C43/203—Making multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/005—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2103/00—Use of resin-bonded materials as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B29K2105/122—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles microfibres or nanofibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2201/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/001—Layered products the layers being loose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to lignocellulose materials which contain one or more lignocrucose-containing substances, microfibrillated cellulose and binders, optionally expanded or expandable plastic particles and optionally additives, and processes for their preparation.
  • wood fiber boards in particular MDF boards, known in which wood fibers were partially replaced by cellulose fibers from waste paper.
  • admixtures of waste paper cellulose fibers to wood fibers of up to 90% were tested.
  • From wood as raw material and material 1970, 28, 3, page 101 to 104 chipboard with admixture of waste paper strips are known.
  • waste paper was shredded in a shredder, 1: 1 mixed with wood chips, glued and pressed into chipboard. There are difficulties in mixing the paper with the wood chips and the mechanical properties leave something to be desired.
  • the present invention was therefore based on the object to remedy the aforementioned disadvantages, in particular to produce lignocellulosic materials with improved mechanical properties. Accordingly, new and improved lignocellulosic materials have been proposed
  • a binder selected from the group consisting of amino resin, phenol formaldehyde resin, organic isocyanate having at least two isocyanate groups or mixtures thereof, optionally with a hardener,
  • microfibrillated cellulose B) 0.01 to 50% by weight of microfibrillated cellulose, C) 1 to 50% by weight of a binder selected from the group consisting of aminoplast resin, phenol-formaldehyde resin, organic isocyanate having at least two isocyanate groups or mixtures thereof, optionally with a hardener,
  • lignocellulosic material means single or multi-layered, ie one to five-layered, preferably one to three-layered, particularly preferably one or three-layered lignocellulose materials.
  • lignocellulose materials may be understood to be veneered chipboard, OSB or fiber materials, in particular wood fiber materials such as LDF, MDF and HDF materials, preferably chipboard or fiber materials, particularly preferably chipboard materials.
  • Materials are u.a. Plates, tiles, moldings, semi-finished products or composites, preferably plates, tiles, moldings or composites, particularly preferably plates.
  • Component A Component A
  • Lignocellulosic substances are substances that contain lignocellulose.
  • the content of lignocellulose can be varied within wide ranges and is generally from 20 to 100% by weight, preferably from 50 to 100% by weight, particularly preferably from 85 to 100% by weight, in particular 100% by weight, of lignocellulose.
  • the term lignocellulose is known to the person skilled in the art.
  • Suitable as one or more lignocellulose-containing substances are, for example, straw, wood-fiber-containing plants, wood or mixtures thereof.
  • a plurality of lignocellulose-containing substances are understood as meaning 2 to 10, preferably 2 to 5, particularly preferably 2 to 4, in particular 2 or 3, different lignocellulose-containing substances.
  • wood fibers or wood particles such as wood layers, wood strips, wood chips, wood dust or mixtures thereof, preferably wood chips, wood fibers, wood dust or mixtures thereof, particularly preferably wood chips, wood fibers or mixtures thereof.
  • wood fibers or wood particles such as wood layers, wood strips, wood chips, wood dust or mixtures thereof, preferably wood chips, wood fibers, wood dust or mixtures thereof, particularly preferably wood chips, wood fibers or mixtures thereof.
  • flax, hemp or mixtures thereof are suitable as wood fiber-containing plants.
  • Starting materials for wood particles or wood fibers are usually thinning woods, industrial timbers and used woods as well as wood fiber-containing plants or plant parts.
  • any type of wood such as soft or hardwood of deciduous or coniferous wood, including from industrial lumber or plantation wood in question, preferably eucalyptus, spruce, beech, pine, larch, linden, poplar, ash, Chestnut, fir or their mixtures, particularly preferably eucalyptus, spruce, beech or their mixtures, in particular eucalyptus, spruce or their mixtures.
  • the lignocellulose-containing substances are comminuted according to the invention as a rule and used as particles or particles.
  • particles are sawdust, wood chips, wood shavings, wood particles, optionally crushed cereal straw, shives, cotton stalks or mixtures thereof, preferably sawdust, wood shavings, wood chips, wood particles, shives or mixtures thereof, particularly preferably sawdust, wood shavings, wood chips, wood particles or their mixtures.
  • the dimensions of the comminuted lignocellulosic materials are not critical and depend on the lignocellulosic material to be produced.
  • Large chips, which are used, for example, for the production of OSB boards are also called strands.
  • the average size of the particles for producing OSB boards, strands is generally 20 to 300 mm, preferably 25 to 200 mm, particularly preferably 30 to 150 mm.
  • Suitable fibers are wood fibers, cellulose fibers, hemp fibers, cotton fibers, bamboo fibers, miscanthus, bagasse or mixtures thereof, preferably wood fibers, hemp fibers, bamboo fibers, miscanthus, bagasse (sugar cane) or mixtures thereof, particularly preferably wood fibers, bamboo fibers or mixtures thereof.
  • the length of the fibers is usually 0.01 to 20 mm, preferably 0.05 to 15 mm, particularly preferably 0.1 to 10 mm.
  • the particles or fibers are usually sorted, i. When only one of the aforementioned varieties (e.g., shavings, wood shavings or wood fibers) is used, they are mixtures whose individual parts, particles or fibers differ in size and shape.
  • the preparation of the desired lignocellulose-containing substances can be carried out by methods known per se (see, for example: M. Dunky, P. Niemz, wood materials and glues, pages 91 to 156, Springer Verlag Heidelberg, 2002).
  • the lignocellulose-containing substances can be obtained by customary methods known to those skilled in the art of drying with the then customary small amounts of water (in a customarily small fluctuation range, so-called "residual moisture"), this water is not taken into account in the weight data of the present invention.
  • the average density of the lignocellulose-containing substances according to the invention is arbitrary and depends only on the lignocellulose-containing substance used and is generally 0.2 to 0.9 g / cm 3 , preferably 0.4 to 0.85 g / cm 3 , particularly preferably at 0.4 to 0.75 g / cm 3 , in particular at 0.4 to 0.6 g / cm 3 .
  • HDF high density fiberboard
  • MDF medium density fibreboard
  • LDF light fibreboard
  • Suitable component B) is microfibrillated cellulose, which is also referred to as microcellulose, (cellulose) microfibrils, nanofibrillated cellulose, nanocellulose or (cellulose) nanofibrils (Cellulose 2010, 17, 459, page 460, right column).
  • microfibrillated cellulose is meant a cellulose which has been defibrillated. This means that the individual microfibrils of the cellulosic fibers have been partially or completely separated from each other.
  • the microfibrillated cellulose has an average fiber length of from 0.1 to 1500 ⁇ m, preferably from 1 to 1500 ⁇ m, more preferably from 500 to 1300 ⁇ m, and at least 15% by weight of the fibers are shorter than 200 ⁇ m.
  • the microfibrillated celluloses generally have a BET surface area of 10 to 500 m 2 / g, preferably 20 to 100 m 2 / g, particularly preferably 30 to 75 m 2 / g.
  • the microfibrillated celluloses generally have a drainability of> 60 SR, preferably> 75 SR, more preferably> 80 SR.
  • the mean fiber length is the weight average fiber length (Lw) determined according to the Tappi standard T271 (Lit: Tappi Journal, 45 (1962), No. 1, pages 38 to 45. The proportion of fibers that do not exceed a certain length will also determined by the Tappi standard T271.
  • the BET surface area of the microfibrillated cellulose can be determined by the following method: An aqueous formulation of the microfibrillated cellulose (suspension, gel) is placed on a frit and washed with tert-butanol. The obtained tert-butanol suspension of the microfibrillated cellulose is transferred from the frit to a chilled metal plate (about 0 ° C.) with glass lid (Lyophilizer, freeze dryer) applied. The sample is dried under cooling overnight. Tert-butanol sublimes slowly and leaves the structured microfibrillated cellulose freeze-dried.
  • the surface is determined by physisorption of nitrogen (measurement in a Surface BET meter (Micromeritics ASAP2420), the nitrogen loading is plotted against the nitrogen partial pressure and evaluated by BET theory).
  • the SR values are determined according to the Schopper-Riegler method as in ISO 5267-1.
  • Cellulose is known per se and / or can be prepared by processes known per se.
  • Microfibrillated cellulose can be made from commercial cellulose or celluloses for the paper industry. Microfibrillated cellulose can be produced in several ways:
  • the microfibrillated cellulose is preferably prepared by method a), b), d), e), particularly preferably by method a), b), d), in particular by method a), b).
  • Suitable cellulose are new or recycled celluloses or mixtures thereof, in particular new or recycled cellulose fibers or mixtures thereof.
  • Wood pulp includes, for example, groundwood such as groundwood or groundwood pulp, thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), semi-pulp, high yield pulp and refiner mechanical pulp (RMP), as well as recovered paper; all from mechanical production.
  • pulps that can be used in bleached or unbleached form.
  • these are sulphate, sulphite, soda and soda pulps; all from chemical production.
  • Bleached pulps also referred to as bleached kraft pulp, are preferably used among the pulps.
  • the substances or fibers mentioned can be used alone or in a mixture.
  • the cellulose can be produced as it is in the abovementioned production processes without or with subsequent purification. preferably without post-cleaning or as it is present in papermaking can be used.
  • fiber-containing raw materials such as cellulose, crude fibers, whole plants containing fibers, or fiber-containing plant components such as stems, as well as annual and perennial plants, woods of all kinds such as softwood or Hardwood, so wood any type of wood such as deciduous or coniferous wood, etc.
  • eucalyptus, spruce, beech pine, larch, linden, poplar, ash, chestnut, fir or their mixtures, preferably eucalyptus, spruce, beech, Pine, larch, linden, poplar, ash, chestnut, fir or their mixtures, particularly preferably eucalyptus, spruce, beech or mixtures thereof, in particular eucalyptus, spruce or mixtures thereof, and paper, paperboard, Cardboard, waste paper, old cardboard and old cardboard.
  • Hemp, flax, reed, cotton, wheat, barley, rye, oats, sugarcane (bagasse), corn stalks, sunflower stalks, sisal or kenaf are suitable as annual plants.
  • fiber-containing agricultural waste such as corn stalks or sunflower stalks can be used as raw materials.
  • cereals such as oat or rice chaff and cereal straw are suitable, for example. of wheat, barley, rye or oats.
  • pulp is understood in this context to be the mechanical or chemical process obtainable mushy mass (mash), having a solids content of 0 to 80 wt .-%, preferably 0.1 to 60 wt .-%, particularly preferably 0, 5 to 50 wt .-%, which originate from the comminution of the aforementioned raw materials.
  • Pulps may also be made from waste and waste paper, alone or in blends with other fibrous materials.
  • the used paper can come from a de-inking process or from an old-corrugated container pulp (OCC). Mixtures of old and new material can also be used.
  • Preferred cellulose-containing fibers contain bleached chemical pulps, preferably bleached kraft pulps, preferably softwood kraft pulps and / or waste paper.
  • the cellulosic fibers used as raw material can be pretreated before use. Such pretreatments may be the removal of toxic or undesirable matter, crushing, hammering, milling, pinning, or washing the material, or combinations thereof.
  • the cellulose-containing fibers are subjected to mechanical shear as starting material as an aqueous mixture.
  • the solids content of the fiber mixture is usually 10 to 100 wt .-%, but normally 10 to 90 wt .-%, preferably 30 to 70 wt .-%, particularly preferably 40 to 60 wt .-%, in particular 50 to 60 wt .-%.
  • Component B) may contain thermostable biocides.
  • Preferred thermostable biocides are selected from the group of 2H-isothiazol-3-one derivatives, glutaraldehyde, pyrithione and its derivatives and benzalkonium chloride.
  • 2H-isothiazol-3-one derivatives are methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone and benzisothiazolinone.
  • Examples of pyrithione derivatives are sodium pyrithione and dipyrite ion.
  • thermostable biocides are selected from the group consisting of methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone and benzisothiazolinone, glutaraldehyde, sodium pyrithione and benzalkonium chloride.
  • Component C is selected from the group consisting of methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone and benzisothiazolinone, glutaraldehyde, sodium pyrithione and benzalkonium chloride.
  • Suitable binders are resins such as phenol-formaldehyde resins, amino resins, organic isocyanates having at least 2 isocyanate groups or mixtures thereof.
  • the resins may be used alone, as a sole resin component or a combination of two or more resin components of the different resins of the group of phenol-formaldehyde resins, aminoplast resins and organic isocyanates having at least 2 isocyanate groups.
  • Phenol-formaldehyde resins are known to the person skilled in the art, see, for example, Kunststoff-Handbuch, 2nd edition, Hanser 1988, Volume 10 "Duroplastics", pages 12 to 40,
  • aminoplast resins it is possible to use all the aminoplast resins known to the person skilled in the art, preferably those known for the production of wood-based materials. Such resins and their preparation are described, for example, in Ullmann's Enzyklopadie der ischen Chemie, 4th, revised and expanded edition, Verlag Chemie, 1973, pages 403 to 424 "Aminoplasts” and Ullmann's Encyclopedia of Industrial Chemistry, Vol. A2, VCH Verlagsgesellschaft, 1985, Pages 1 15 to 141 "Amino Resins" as well as in M. Dunky, P.
  • the setting of the desired molar ratio of aldehyde, preferably formaldehyde, to the optionally partially substituted with organic radicals amino group can also by adding -Nh group-carrying monomers to formaldehyde-enriched finished, preferably commercial, Aminoplastharzen done.
  • Nh group-carrying monomers are preferably urea, melamine or mixtures thereof, more preferably urea.
  • Preferred amino resins are polycondensation products of compounds having at least one, optionally partially substituted by organic radicals, carbamide group (the carbamide group is also referred to as carboxamide) and an aldehyde, preferably formaldehyde understood; most preferably urea-formaldehyde resins (UF-resins), melamine-formaldehyde resins (MF-resins) or melamine-containing urea-formaldehyde resins (MUF-resins), in particular urea-formaldehyde resins, for example Kaurit ® glue types from BASF SE.
  • carbamide group the carbamide group is also referred to as carboxamide
  • aldehyde preferably formaldehyde understood
  • urea-formaldehyde resins urea-formaldehyde resins
  • MF-resins melamine-formaldehyde resins
  • UMF-resins mel
  • very preferred aminoplast resins are polycondensation products of compounds having at least one, also partially substituted by organic radicals, amino group and aldehyde, wherein the molar ratio of aldehyde to optionally partially substituted with organic radicals amino group in the range of 0.3: 1 to 1: 1 , preferably 0.3: 1 to 0.6: 1, particularly preferably 0.3: 1 to 0.45: 1, very particularly preferably 0.3: 1 to 0.4: 1.
  • the aminoplast resins mentioned are usually suspended in liquid form, usually in a liquid medium, preferably in aqueous suspension or else as solid.
  • the solids content of the aminoplast resin suspensions is usually from 25 to 90% by weight, preferably from 50 to
  • the solids content of the aminoplast resin in aqueous suspension can be determined according to Günter Zeppenfeld, Dirk Grunwald, adhesives in the wood and furniture industry, 2nd edition, DRW-Verlag, page 268.
  • To determine the solids content of aminoplast glues 1 g of aminoplast glue is weighed exactly into a weighing pan, finely distributed on the bottom and dried for 2 hours at 120 ° C. in a drying oven. After tempering to room temperature in a desiccator, the residue is weighed and calculated as a percentage of the initial weight.
  • the weight of the binder refers with respect to the aminoplast component in the binder on the solids content of the corresponding component (determined by evaporation of water at 120 ° C, within 2 h after Günter Zeppenfeld, Dirk Grunwald, adhesives in the wood and furniture industry, 2 Edition, DRW-Verlag, page 268) and with regard to the isocyanate, in particular the PMDI, to the isocyanate component per se, that is, for example, without a solvent or emulsifier.
  • Organic isocyanates in particular the PMDI
  • Suitable organic isocyanates are organic isocyanates having at least two isocyanate groups or mixtures thereof, in particular all those skilled in the art, preferably the known for the production of wood materials or polyurethanes, organic isocyanates or mixtures thereof.
  • Such organic isocyanates and their preparation and use are described, for example, in Becker / Braun, Kunststoff Handbuch, 3rd revised edition, Volume 7 "Polyurethane", Hanser 1993, pages 17 to 21, pages 76 to 88 and pages 665 to 671.
  • Preferred organic Isocyanates are oligomeric isocyanates having 2 to 10, preferably 2 to 8 monomer units and an average of at least one isocyanate group per monomer unit or mixtures thereof, particularly preferably the oligomeric organic isocyanate PMDI ("Polymered Methylendiphenylendiisocyanat") which is obtainable by condensation of formaldehyde with aniline and phosgenation of the isomers and oligomers formed in the condensation (see, for example, Becker / Braun, Kunststoff Handbuch, 3rd revised edition, Volume 7 "Polyurethane", Hanser 1993, pages 18 last paragraph to page 19, second paragraph and page 76, fifth paragraph), BASF SE very particularly preferably products of LUPRANAT ® type series, in particular sondere LUPRANAT ® M 20 BASF SE FB. Hardener in component C
  • the binder C) may contain hardeners known to those skilled in the art or mixtures thereof.
  • Suitable hardeners for aminoplast resins or phenolformaldehyde resins are those which catalyze the further condensation, such as acids or their salts or aqueous solutions of these salts.
  • Suitable acids are inorganic acids such as HCl, HBr, Hl, H 2 SO 3, H 2 SO 4, phosphoric acid, polyphosphoric acid, nitric acid, sulfonic acids, for example p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, carboxylic acids such as Cr to Cs-carboxylic acids, for example formic acid, acetic acid, Propionic acid or mixtures thereof, preferably inorganic acids such as HCl, H2SO3, H2SO4, phosphoric acid, polyphosphoric acid, nitric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, carboxylic acids such as C to Cs carboxylic acids, for example formic acid, acetic acid, particularly preferably inorganic acids such as H2SO4, Phosphoric acid, ni
  • Suitable salts are halides, sulfites, sulfates, hydrogen sulfates, carbonates, hydrogencarbonates, nitrites, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates, propionates, preferably sulfites, carbonates, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates , Propionates, particularly preferred sulfites, nitrates, sulfonates, salts of carboxylic acids such as formates, acetates, propionates, protonated, primary, secondary and tertiary aliphatic amines, alkanolamines, cyclic, aromatic amines such as d- to Cs-Aminejsopropylamin, 2-ethylhexylamine, Di- (2-ethylhexyl) amine, diethylamine,
  • Particularly suitable salts are: ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, ammonium methanesulfonate,
  • the salts are used in the form of their aqueous solutions.
  • aqueous solutions are understood as meaning dilute, saturated, supersaturated and also partially precipitated solutions, as well as saturated solutions having a solids content of insoluble salt.
  • Phenol-formaldehyde resins may also be cured alkaline, preferably with carbonates or hydroxides, such as potassium carbonate and sodium hydroxide.
  • organic isocyanate hardeners with at least two isocyanate groups can be subdivided into four groups: amines, further bases, metal salts and organometallic compounds, preference being given to amines.
  • Such hardeners are described, for example, in Michael Szycher, Szycher's Handbook of Polyurethanes, CRC Press, 1999, pages 10-1 to 10-20.
  • compounds which greatly accelerate the reaction of reactive hydrogen atoms, in particular hydroxyl groups, containing compounds with the organic isocyanates are also suitable.
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyldiaminodiethyl ether, bis (dimethylaminopropyl) urea, N-methyl or N-ethylmorpholine, N-cyclohexylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylbutanediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylhexanediamine-1, 6, pentamethyldiethylenetriamine , Dimethylpiperazine, N-dimethylaminoethylpiperidine, 1, 2-d
  • 1, 4-diazabicyclo (2,2,2) octane (Dabco) and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy) ethanol, N, N ', N "tris (dialkylaminoalkyl) hexahydrotriazines, eg N, ⁇ ', N" - tris- (dimethylaminopropyl) -s-hexahydrotriazine, and triethylenediamine.
  • alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyldiethanolamine, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy) ethanol, N, N ', N "tris (dialkylaminoalkyl) he
  • Suitable metal salts are salts of metals such as iron (II) chloride, zinc chloride, lead octoate and preferably tin salts such as tin dioctoate.
  • Suitable organometallic compounds are organometallic salts, such as tin dioctoate, tin diethyl hexoate and dibutyltin dilaurate, and in particular mixtures of tertiary amines and organic tin salts.
  • Suitable further bases are amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, alkali metal hydroxides, such as sodium hydroxide and alkali metal alkoxides, such as sodium methylate and potassium isopropylate, and alkali metal salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups.
  • amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine
  • tetraalkylammonium hydroxides such as tetramethylammonium hydroxide
  • alkali metal hydroxides such as sodium hydroxide and alkali metal alkoxides, such as sodium methylate and potassium isopropylate
  • alkali metal salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups.
  • curing agents for aminoplast resins can be found in M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer 2002, pages 265 to 269
  • hardeners for phenolformaldehyde resins can be found in M. Dunky, P. Niemz, Holzwerkstoffe und Glue, Springer 2002 , Pages 341 to 352
  • hardeners for organic isocyanates having at least 2 isocyanate groups can be found in M. Dunky, P. Niemz, wood materials and glues, Springer 2002, pages 385-391.
  • Component D) are expanded plastic particles which are optionally coated with a binder.
  • Expanded plastic particles preferably expanded thermoplastic particles
  • expandable plastic particles preferably expandable thermoplastic particles. Both are based on or consist of polymers, preferably thermoplastic polymers, which can be foamed. These are known to the person skilled in the art.
  • polystyrene polystyrene resin
  • polystyrene polystyrene resin
  • PVC hard and soft
  • polycarbonates polystyrene resins
  • polyisocyanurates polycarbodiimides
  • polyacrylimides and polymethacrylimides polyamides
  • polyurethanes aminoplast resins and phenolic resins
  • polystyrene homopolymers also referred to below as "polystyrene”
  • styrene polymer styrene polymer
  • styrene copolymers C 2 -C 10 -olefin homopolymers, C 2 -C 10 -olefin copolymers, polyesters or mixtures thereof, preferably PVC (hard and soft), polyurethanes, styrene homopolymer, styrene copolymer or mixtures thereof, particularly preferably styrene homopolymer , Styrene copolymer or mixtures thereof, in particular styrene homopolymer, styrene copolymer or mixtures thereof.
  • PVC hard and soft
  • polyurethanes styrene homopolymer, styrene copolymer or mixtures thereof, particularly preferably styrene homopolymer , Styrene copolymer or mixtures thereof, in particular styrene homopolymer, styrene cop
  • the preferred or particularly preferred expandable styrene polymers or expandable styrene copolymers described above have a relatively low content of blowing agent. Such polymers are also referred to as "low blowing agent.”
  • low blowing agent A well-suited process for producing low-blowing expandable polystyrene or expandable styrenic copolymer is described in US-A-5,112,875, which is incorporated herein by reference.
  • styrene copolymers can also be used.
  • these styrene copolymers have at least 50% by weight, preferably at least 80% by weight, of copolymerized styrene.
  • ⁇ -methyl styrene, ring-halogenated styrene, acrylonitrile, esters of acrylic or methacrylic acid of alcohols having 1 to 8 carbon atoms, N-vinylcarbazole, maleic acid (anhydride), (meth) acrylamides and / or vinyl acetate into consideration.
  • the polystyrene and / or styrene copolymer in copolymerized form contain a small amount of a chain branching, d. H. a compound having more than one, preferably two, double bonds, such as divinylbenzene, butadiene and / or butanediol diacrylate.
  • the splitter is generally sold in quantities of 0.0005 to
  • Mixtures of different styrene (co) polymers can also be used.
  • styrene homopolymers or styrene copolymers are glass clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene- ⁇ -methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS), Methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE) used.
  • GPPS glass clear polystyrene
  • HIPS impact polystyrene
  • A-IPS anionically polymerized polystyrene
  • styrene polymers Preference is given to styrene polymers, styrene copolymers or styrene homopolymers having a molecular weight in the range from 70,000 to 400,000 g / mol, particularly preferred
  • Such polystyrene and / or styrene copolymer can be prepared by all known in the art polymerization process, see, for. Ullmann's Encyclopedia, Sixth Edition, 2000 Electronic Release or Kunststoff-Handbuch 1996, Volume 4 "Polystyrene", pages 567 to 598.
  • the expanded plastic particles consist of different polymer types, ie polymer types which are based on different monomers, for example polystyrene and polyethylene or polystyrene and homopolypropylene or polyethylene and homopolypropylene, these may be present in different weight ratios, which, however, are not critical.
  • the expanded plastic particles are generally in the form of spheres or beads having an average diameter of 0.25 to 10 mm, preferably 0.4 to 8.5 mm, particularly preferably 0.4 to 7 mm, in particular in the range of 1, 2 used to 7 mm and advantageously have a small surface area per volume, for example in the form of a spherical or elliptical particle.
  • the expanded plastic particles are advantageously closed-cell.
  • the off-set to DIN-ISO 4590 is usually less than 30%.
  • the expanded plastic particles have a bulk density of from 10 to 150 kg / m 3 , preferably from 30 to 100 kg / m 3 , particularly preferably from 40 to 80 kg / m 3 , in particular from 50 to 70 kg / m 3 .
  • the bulk density is usually determined by weighing a volume filled with the bulk material.
  • the expanded plastic particles usually have, if at all, only a small content of propellant.
  • the content of blowing agent in the expanded plastic particle is generally in the range of 0 to 5.5 wt .-%, preferably 0 to 3 wt .-%, preferably 0 to 2.5 wt .-%, particularly preferably 0 to 2 wt. -%, in each case based on the expanded polystyrene or expanded styrene copolymer.
  • 0 wt .-% means herein that no propellant can be detected by the usual detection methods.
  • These expanded plastic particles can be used further without or with, preferably without further measures for blowing agent reduction and particularly preferably without further intermediate steps for the preparation of the lignocellulose-containing substance.
  • the expandable polystyrene or expandable styrene copolymer or the expanded polystyrene or expanded styrene copolymer usually has an antistatic coating.
  • the expanded plastic particles
  • Compact expandable plastic particles usually solids that generally have no cell structure containing an expansible medium (also called “propellant”), are expanded by the action of heat or pressure change (often referred to as “frothing”).
  • propellant expands, the particles increase in size and cell structures arise.
  • pre-expanders This expansion is generally carried out in conventional frothing devices, often referred to as "pre-expanders.” Such pre-expanders can be fixed in place or mobile.
  • the expansion can be carried out in one or more stages. As a rule, in the single-stage process, the expandable plastic particles are readily expanded to the desired final size.
  • the expandable plastic particles are first expanded to an intermediate size and then expanded in one or more further stages over a corresponding number of intermediate sizes to the desired final size.
  • the expansion is carried out in one stage.
  • expanded polystyrene as component D) and / or expanded styrene copolymer as component D) are generally the expandable styrene or expandable styrene copolymers in a known manner by heating to temperatures above its softening point, for example with hot air or preferably steam and or pressure change expanded (often referred to as "foamed"), as described for example in Kunststoff Handbuch 1996, Volume 4 "polystyrene", Hanser 1996, pages 640-673 or US-A-5,112,875.
  • the expandable polystyrene or expandable styrene copolymer is generally obtainable in a manner known per se by suspension polymerization or by extrusion processes as described above. During expansion, the propellant expands, the polymer particles increase in size and cell structures are formed.
  • the production of the expandable polystyrene and / or styrene copolymer is generally carried out in a manner known per se by suspension polymerization or by extrusion processes.
  • suspension polymerization styrene, if appropriate with the addition of further comonomers, is polymerized in aqueous suspension in the presence of a customary suspension stabilizer by means of free-radical-forming catalysts.
  • the blowing agent and, if appropriate, further additives can be introduced during the polymerization or added to the batch in the course of the polymerization or after the end of the polymerization.
  • the resulting peribular, impregnated with blowing agent, expandable styrene polymers are separated after the polymerization from the aqueous phase, washed, dried and sieved.
  • the blowing agent is mixed for example via an extruder in the polymer, conveyed through a nozzle plate and granulated under pressure to particles or strands.
  • the resulting expanded plastic particles or the coated expanded plastic particles can be stored and transported.
  • blowing agents are all blowing agents known to those skilled in the art, for example aliphatic C3 to C10 hydrocarbons, such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane and / or hexane and its isomers, alcohols, ketones, Esters, ethers, halogenated hydrocarbons or mixtures thereof,
  • n-pentane isopentane, neopentane, cyclopentane or a mixture thereof, particularly preferably commercially available pentane isomer mixtures of n-pentane and iso-pentane.
  • the content of blowing agent in the expandable plastic particles is generally in the range of 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, preferably 0.1 to 4 wt .-%, particularly preferably 0.5 to 3.5 wt .-%, each based on the propellant-containing expandable polystyrene or styrene copolymer.
  • Suitable coating compositions for the expandable or expanded plastic particles are all compounds of components B and C and compounds K which form a sticky layer, or mixtures thereof, preferably all compounds of component C and compounds K which form a sticky layer are particularly preferred all compounds of component C.
  • coating agent and component C in the lignocellulosic material may be the same or different, preferably the same.
  • Suitable compounds K which form a sticky layer are polymers based on monomers such as vinylaromatic monomers, such as ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1,2-diphenylethylene, 1, 1-diphenylethylene, alkenes such as ethylene or propylene, dienes such as 1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2,3- Dimethylbutadiene, isoprene, piperylene or isoprene, ⁇ -.beta.-unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, their esters, in particular alkyl esters, such as C 1 to C 10 alkyl esters of acrylic acid, in particular the butyl ester, preferably n-butyl acrylate, and the C 1 - to
  • These polymers may optionally contain from 1 to 5% by weight of comonomers, such as (meth) acrylonitrile, (meth) acrylamide, urido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, acrylamide derivatives. pansulfonic acid, methylolacrylamide or the sodium salt of vinylsulfonic acid.
  • comonomers such as (meth) acrylonitrile, (meth) acrylamide, urido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, acrylamide derivatives.
  • pansulfonic acid methylolacrylamide or the sodium salt of vinylsulfonic acid.
  • These polymers are preferably composed of one or more of the monomers styrene, butadiene, acrylic acid, methacrylic acid, C 1 - to C 4 -alkyl acrylates, C 1 - to C 4 -alkyl methacrylates, acrylamide, methacrylamide and methylolacrylamide.
  • acrylate resins particularly preferably in the form of the aqueous polymer dispersion, and homo-oligomers or homopolymers of ⁇ - ⁇ -unsaturated carboxylic acids or their anhydrides and co-oligomers or copolymers of ⁇ - ⁇ -unsaturated carboxylic acids and / or their anhydrides are also suitable ethylenically unsaturated co-monomers.
  • Suitable polymer dispersions are obtainable, for example, by free-radical emulsion polymerization of ethylenically unsaturated monomers, such as styrene, acrylates, methacrylates or mixtures thereof, as described in WO-A-00/50480, preferably pure acrylates or styrene acrylates, which are selected from the monomers styrene, n Butyl acrylate, methyl methacrylate (MMA), methacrylic acid, acrylamide or methylolacrylamide.
  • ethylenically unsaturated monomers such as styrene, acrylates, methacrylates or mixtures thereof, as described in WO-A-00/50480, preferably pure acrylates or styrene acrylates, which are selected from the monomers styrene, n Butyl acrylate, methyl methacrylate (MMA), methacrylic acid, acrylamide or methylolacryl
  • the preparation of the polymer dispersion or suspension can be carried out in a manner known per se, for example by emulsion, suspension or dispersion polymerization, preferably in the aqueous phase. It is also possible to prepare the polymer by solution or bulk polymerization, optionally dicing and then dispersing the polymer particles in water in a customary manner.
  • the coating composition can be brought into contact with the expandable plastic particle ("Variant I”) or with the expanded plastic particle ("Variant II”); Preferably variant (II) is used.
  • coated plastic particles according to the invention can be produced, for example, by a) plastic particles, preferably non-expandable plastic particles, melting, one or more coating agents and propellants in any order, mixed as homogeneously as possible and foamed into foam particles,
  • expandable plastic particles coated during or after the pre-foaming with one or more coating agents can be brought into contact with the customary processes, for example by spraying, dipping, wetting or tumbling the expandable or expanded plastic particles with the coating agent at a temperature of 0 to 150 ° C., preferably 10 to 120 ° C., particularly preferably 15 to 1 10 ° C and a pressure of 0.01 to 10 bar, preferably 0.1 to 5 bar, more preferably at atmospheric pressure (atmospheric pressure);
  • the coating agent is added in the so-called pre-foamer under the aforementioned conditions.
  • the lignocellulose materials according to the invention may be known to those skilled in and commercially available additives as component E in amounts of 0 to 68 wt .-%, preferably 0 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-%, in particular 1 to 3 wt .-% contain.
  • Suitable additives are, for example, water repellents such as paraffin emulsions, antifungal agents, formaldehyde scavengers such as urea or polyamines, and flame retardants, extenders, fillers. Further examples of additives can be found in M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer 2002, pages 436 to 444.
  • the total amount of dry matter of the microfibrillated cellulose, based on the dry matter of the lignocellulose-containing substances, is generally between 0.01 to 50 wt .-%, preferably between 0.05 and 40 wt .-%, particularly preferably between 0.1 and 30% by weight.
  • the total amount of the binder C), based on the lignocellulose-containing substances is generally in the range of 1 to 50 wt .-%, preferably 2 to 15 wt .-%, particularly preferably 3 to 10 wt .-%, wherein the amount a) of the phenol-formaldehyde resin, based on the lignocellulose-containing substances, generally in the range from 0 to 50% by weight, preferably 4 to 20% by weight, particularly preferably 5 to 15% by weight,
  • aminoplast resin (calculated as a solid, based on the lignocellulose-containing substances usually in the range of 0 to 45 wt .-%, preferably 4 to 20 wt .-%, particularly preferably 5 to 15 wt .-% and
  • c) of the organic isocyanate based on the lignocellulose-containing substances is usually in the range of 0 to 7 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.5 to 4 wt .-%.
  • the total amount of the coating agent on the expanded plastic particles D), based on the amount of uncoated plastic particles, is in the range from 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight.
  • the optionally coated, expanded plastic particles D) are usually in a practically unmelted state even after pressing to the lignocellulosic material, preferably wood material, preferably multilayer lignocellulosic material, more preferably multilayer wood material.
  • plastic particles D) have generally not penetrated into the lignocellulose particles or impregnated them, but are distributed between the lignocellulosic particles.
  • the plastic particles D) can be separated from the lignocellulose by physical methods, for example after comminution of the lignocellulose material.
  • the total amount of the coated, expanded plastic particles D), based on the lignocellulose-containing, preferably wood-containing material, is in the range from 0 to 25 wt .-%, preferably 0 to 20 wt .-%, particularly preferably 0 to 15 wt .-%.
  • the present invention further relates to a process for producing a single- or multi-layered lignocellulosic material containing at least three layers, wherein either only the middle layer or at least a portion of the middle layers contain a lignocellulosic material as defined above or except the middle layer or at least one Part of the middle layers at least one further layer containing a lignocellulose-containing substance as defined above, wherein the components for the individual layers überpetit füret and pressed under elevated temperature and elevated pressure.
  • the average density of the multilayer, preferably of the three-layered, lignocellulose material according to the invention, preferably wood material according to the invention is generally not critical.
  • higher density multilayered, preferably inventive three-layered, lignocellulosic materials according to the invention usually have a mean density in the range of at least 600 to 900 kg / m 3 , preferably 600 to 850 kg / m 3 , particularly preferably 600 to 800 kg / m 3 .
  • low-density multilayer, preferably inventive, three-layer, lignocellulosic materials according to the invention usually have a mean density in the range of 200 to 600 kg / m 3 , preferably 300 to 600 kg / m 3 , particularly preferably 350 to 500 kg / m 3 .
  • Preferred parameter ranges and preferred embodiments with regard to the average density of the lignocellulose-containing, preferably wood-containing substance and with regard to the components and their preparation processes A), B), C), D) and E) and the combination of the features correspond to those described above.
  • Middle layers in the sense of the invention are all layers that are not the outer layers.
  • the microfibrillated cellulose can be applied in various ways: a) spraying a liquid MFC formulation (solution, dispersion, suspension) onto the wood chips / fibers or
  • the spraying of a liquid MFC formulation on wood chips / fibers can be done before or after the application of the binder C).
  • the solvent used is water, preferably tap water, deionized water, demineralized water or distilled water.
  • concentration of MFC in the aqueous formulation is chosen so that it can still be sprayed onto the wood chips without any problems and the MFC spreads evenly over the chips.
  • the solids content of the MFC formulation is between 0.01 and 20%, preferably between 0.05 and 15%, particularly preferably between 0.1 and 10%.
  • the addition of the solid MFC to the wood chips / fibers can be done before or after the application of the binder C).
  • the MFC used should be powdery and pourable.
  • the amount of MFC based on the amount of wood chips / fibers is between 0.01 and 50 wt .-%, preferably between 0.1 and 30 wt .-%, particularly preferably between 0.1 and 15 wt .-%.
  • the MFC is formulated in the binder C), so that
  • the binder C) is completely absorbed by the MFC and a solid formulation is formed.
  • the concentration of MFC in the formulation is selected so that it still has problematic los can be sprayed onto the wood chips / fibers.
  • the amount of MFC based on the solids content of the binder is preferably between 0.001 and 20 wt .-%, more preferably between 0.01 and 10 wt .-%, particularly preferably between 0.1 and 5 wt .-%.
  • the MFC is mixed with just enough binder C) that the resulting solid is still just powdery and free-flowing.
  • the MFC is preferably added as granules in the production of the wood chips / fibers.
  • the MFC in the production of wood chips in or before the Zerspaner or in the production of wood fibers in or before the refiner added to the wood chips.
  • the amount of MFC based on the amount of wood chips / fibers is between 0.01 and 50 wt .-%, preferably between 0.1 and 30 wt .-%, particularly preferably between 0.5 and 15 wt .-%.
  • the multilayer lignocellulosic material according to the invention preferably multilayer wood material, preferably contains three lignocellulosic layers, preferably wood pulp layers, the outer cover layers generally being thinner overall than the inner (s)
  • the binder used for the outer layers is usually an amino-plastharz, such as urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF), melamine-urea-formaldehyde resin (MUF) or the inventive binder C).
  • the binder used for the outer layers is an aminoplast resin, more preferably a urea-formaldehyde resin, most preferably an aminoplast resin wherein the molar formaldehyde to -NH 2 group ratio is in the range of 0.3: 1 to 3: 1.
  • the outer layers (usually called “cover layers”) contain no expanded plastic particles D.
  • the thickness of the multilayered lignocellulosic material of the invention, preferably multilayer wood material varies with the field of application and is typically in the range of 0.5 to 100 mm , preferably in the range of 10 to 40 mm, in particular 12 to 40 mm.
  • the methods for producing multilayer wood-based materials are known in principle and, for example, in M. Dunky, P. Niemz, wood materials and glues, Springer 2002, pages 91 to 150 described.
  • component D is first foamed from expandable plastic particles and optionally coated with coating agent.
  • the chips After cutting the wood, the chips are dried. Thereafter, if necessary, coarse and fines are removed. The remaining chips are sorted by sieving or sifting in the air stream. The coarser material is used for the middle layer, the coarser material for the cover layers.
  • the cover shavings are separated from the middle layer shavings with component B) as 2.5% by weight aqueous suspension, component C), hardener, these hardeners are preferably added shortly before the use of the component C, and optionally glues component E, or mixed.
  • This mixture is referred to below as a cover layer material.
  • the middle layer chips are separated from the outer layer chips with the component B) as 2.5 wt .-% aqueous suspension, optionally with the optionally coated component D), component C), hardener, these hardeners are preferred shortly before the use of component C) added, and optionally gluing component E, or mixed. This mixture is then referred to as middle layer material.
  • the cover layer material is scattered on the forming belt, then the middle layer material - containing the coated components B), C) and optionally D) and E) - and finally again cover layer material.
  • the cover layer material is divided so that both cover layers contain approximately the same amount of material.
  • the three-layer chip cake thus produced is precompressed cold (usually at room temperature) and then pressed hot.
  • the pressing can be carried out by all methods known to the person skilled in the art. Usually, the wood particle cake is pressed at a press temperature of 150 to 230 ° C to the desired thickness.
  • the pressing time is normally 3 to 15 seconds per mm plate thickness. This gives a three-layer chipboard.
  • the mechanical strength can be determined by measuring the transverse tensile strength according to EN 319.
  • microfibrillated cellulose to the wood chips / fibers causes an improvement in the transverse tensile strength and allows the production of lignocellulose materials with a reduced total amount of binder. Furthermore, light lignocellulose materials can be produced.
  • Lignocellulosic materials in particular multilayer wood materials, are a cost-effective and resource-saving alternative to solid wood and are of great importance and are used for the production of objects of all kinds and in the construction sector, in particular for the production of furniture and furniture parts (in furniture), packaging materials, laminate flooring and as building materials, in building construction or in interior work or in motor vehicles.
  • microfibrillated cellulose is suitable for the production of lignocellulose-containing shaped bodies (use).
  • microfibrillated cellulose used was prepared according to the process described in WO-A-2010 / 14971.1.
  • Preparation of a dispersion of component B) 3800 g of water were stirred with 200 g of microfibrillated cellulose (50% solids content) using an Ultra Turrax T50 from Janke & Kunkel until a homogeneous suspension was obtained. Shortly before the suspension was used, the homogeneity of the suspension was checked again and, if necessary, reconstituted by stirring again.
  • glues was urea-formaldehyde glue (glue Kaurit ® 347 of BASF SE) was used. The solids content was adjusted in each case with water to 67 wt .-%.
  • a glue liquor comprising 100 parts chewing rit ® -Leim were applied 347 and 1 part of a 52% aqueous solution of ammonium nitrate, 0.5 parts of urea, 0.7 parts of a 44% aqueous paraffin dispersion and 40 parts water.
  • microfibrillated cellulose treated and glued chips were applied in a 30x30 cm mold as follows:
  • topcoat material half of the topcoat material was sprinkled into the mold. Subsequently, 50 to 100% of the middle layer material was layered over it. Finally, the second half of the overlay material was layered over it and precompressed cold. It was then pressed in a hot press (pressing temperature 210 ° C, pressing time 120 s). The nominal thickness of the plate was 16mm in each case.
  • the density was determined 24 hours after production. For this purpose, the ratio of mass and volume of a specimen was determined at the same moisture content.
  • the square test specimens had a side length of 50 mm, with an accuracy of 0.1 mm.
  • the thickness of the test piece was measured in its center with an accuracy of 0.05 mm.
  • the scale for determining the specimen mass had an accuracy of 0.01 g.
  • the apparent density p (kg / m 3 ) of a test specimen was calculated according to the following formula: Where:
  • bi, b2 and d are the width and thickness of the specimen, in millimeters.
  • the determination of the transverse tensile strength is perpendicular to the plate plane.
  • the test specimen was loaded with a uniformly distributed tensile force until breakage.
  • the square specimens had a side length of 50 mm, with an accuracy of 1 mm, and angles of exactly 90 °. Furthermore, the edges were clean and straight.
  • the test specimens were bonded to the yokes by means of a suitable adhesive, for example an epoxy resin, and dried for at least 24 hours in a climatic chamber at 20 ° C. and 65% atmospheric humidity.
  • the prepared test specimen was then clamped self-aligning in the testing machine on both sides with a shaft joint and then loaded at a constant speed until breakage and measured the force required for it.
  • the determination of the bending strength was carried out by applying a load in the middle of a two-point test specimen.
  • the test piece had a width of 50 mm and a length of 20 times the nominal thickness plus 50 mm, but at most 1 050 mm and a minimum of 1 50 mm.
  • the test specimen was then placed flat on two supports, the distance between the centers was twenty times the thickness of the specimen and then loaded in the middle with a force to break and measured this force.
  • b is the width of the specimen in millimeters
  • t is the thickness of the specimen in millimeters.
  • the determination of the screw withdrawal resistance was made by measuring the force required to pull a screw parallel to the axis out of the test piece.
  • the square test specimens had a side length of 75 mm, with an accuracy of 1 mm.
  • pilot holes, diameter 2.7 mm ( ⁇ 0.1 mm), depth 1.9 ( ⁇ 1 mm), were drilled perpendicular to the surface of the test specimen at the center of the surface.
  • a steel screw with nominal size 4.2 mm ⁇ 38 mm, with a ST 4.2 thread in accordance with ISO 1478 and a thread pitch of 1.4 mm was inserted into the test specimen for the test, so that 1 5 mm ( ⁇ 0 , 5 mm) of the complete thread were introduced.
  • the test specimen was mounted in a metal frame and a clamp was applied to the underside of the screw head a force and measured the maximum force at which the screw was pulled out.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Forests & Forestry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paper (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne de nouveaux matériaux, améliorés, à base de lignocellulose, qui contiennent A) 30 à 98,99 % en poids d'une ou de plusieurs substances contenant de la lignocellulose, B) 0,01 à 50 % en poids de cellulose microfibrillée, C) 1 à 50 % en poids d'un liant choisi dans le groupe constitué par une résine d'aminoplaste, une résine de phénolformaldéhyde, un isocyanate organique comprenant au moins deux groupes isocyanate ou leurs mélanges, le cas échéant avec un durcisseur, D) 0 à 25 % en poids de particules expansées de matériau synthétique présentant une densité apparente dans la plage de 10 à 150 kg/m3, et E) 0 à 68% en poids d'additifs.
EP14777094.5A 2013-10-10 2014-09-29 Matériaux à base de lignocellulose contenant de la cellulose défibrillée Active EP3055453B1 (fr)

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EP14777094.5A EP3055453B1 (fr) 2013-10-10 2014-09-29 Matériaux à base de lignocellulose contenant de la cellulose défibrillée

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EP13188006 2013-10-10
PCT/EP2014/070785 WO2015052028A1 (fr) 2013-10-10 2014-09-29 Matériaux à base de lignocellulose contenant de la cellulose défibrillée
EP14777094.5A EP3055453B1 (fr) 2013-10-10 2014-09-29 Matériaux à base de lignocellulose contenant de la cellulose défibrillée

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EP3055453A1 true EP3055453A1 (fr) 2016-08-17
EP3055453B1 EP3055453B1 (fr) 2023-11-22
EP3055453C0 EP3055453C0 (fr) 2023-11-22

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US (1) US20160257814A1 (fr)
EP (1) EP3055453B1 (fr)
JP (1) JP2016533918A (fr)
KR (1) KR20160068890A (fr)
CN (1) CN105612285A (fr)
AR (1) AR097985A1 (fr)
AU (1) AU2014334089A1 (fr)
BR (1) BR112016007573A2 (fr)
CA (1) CA2926134A1 (fr)
CL (1) CL2016000831A1 (fr)
ES (1) ES2973835T3 (fr)
PL (1) PL3055453T3 (fr)
WO (1) WO2015052028A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA201592168A1 (ru) * 2013-05-14 2016-05-31 Спк Санфлауэр Плэстик Компаунд Гмбх Продукт из биоматериала на основе кожуры семян подсолнечника или шелухи семян подсолнечника
US10661472B2 (en) 2014-12-09 2020-05-26 Basf Se Method for producing multi-layered lignocellulose materials having a core with special properties and at least one upper and one lower cover layer
BR112017019184B1 (pt) * 2015-03-09 2022-03-03 Investigaciones Forestales Bioforest S.A Método para produzir placas mdf, painéis de fibra e de partículas a partir de fibras celulósica
US20220242007A1 (en) * 2016-03-21 2022-08-04 Bondcore öU Composite wood panels with corrugated cores and method of manufacturing same
WO2017216090A1 (fr) * 2016-06-14 2017-12-21 Basf Se Détermination de la forme tridimensionnelle de particules lignocellulosiques
JP7017896B2 (ja) * 2016-09-30 2022-02-09 群栄化学工業株式会社 木質ボード用バインダー組成物、木質ボード及びその製造方法
PL3672771T3 (pl) * 2017-08-23 2023-10-30 Basf Se Sposób wytwarzania materiałów lignocelulozowych w obecności kaprolaktamu i jego oligomerów
JP6448738B1 (ja) * 2017-09-29 2019-01-09 大建工業株式会社 高密度木質積層材の製造方法
EP3735443B1 (fr) * 2018-01-07 2022-03-30 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd Pate de bois et objets fabriques a partir de celles-ci
EP3747614A1 (fr) * 2019-06-04 2020-12-09 Lenzing Aktiengesellschaft Procédé de fourniture d'une matière de départ traitée contenant de la cellulose ayant une répartition de longueur de fibre prédéfinie
EP3748071A1 (fr) * 2019-06-04 2020-12-09 Lenzing Aktiengesellschaft Traitement commun d'une matière première lignocellulosique et d'un produit sans lignine contenant de la cellulose
EP3882928B1 (fr) * 2020-03-17 2023-11-15 Hitachi Energy Ltd Mfc/nc dans les cartes de transformateurs utilisées dans les transformateurs de puissance
KR102215573B1 (ko) * 2020-04-24 2021-02-15 황인준 내충격성이 우수한 합성목재
KR102160383B1 (ko) * 2020-05-28 2020-09-29 황인준 충격흡수 가능한 합성목재 데크구조
IL303204A (en) * 2020-12-02 2023-07-01 Evonik Operations Gmbh Adhesion of particles containing a blowing agent based on polyamides or polyacrylates
US20220242006A1 (en) * 2021-01-15 2022-08-04 Innotech Alberta Inc. Cellulose Particle Mold Release Layer
CA3224279A1 (fr) * 2021-07-02 2023-01-05 Caroline GAMBICHLER Bande de joint applicable par pulverisation pour constructions de cloison seche
US20230167607A1 (en) * 2021-08-24 2023-06-01 W.R. Meadows, Inc. Fiberboard manufactured with cellulose nanofibrils as a binder and method of making same
CN117230542A (zh) * 2023-09-25 2023-12-15 天津永续新材料有限公司 一种磷酸化纤维素纳米纤维及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI126046B (fi) * 2009-04-20 2016-06-15 Elastopoli Oy Komposiittivälituote ja menetelmä sen muodostamiseksi
GB0908401D0 (en) * 2009-05-15 2009-06-24 Imerys Minerals Ltd Paper filler composition
WO2010149711A2 (fr) * 2009-06-24 2010-12-29 Interface International B.V. Et Al Procédé et appareil de défibrage de fibres de cellulose
AU2010283880B2 (en) * 2009-08-13 2015-03-26 Basf Se Light lignocellulosic materials having good mechanical properties
JP5622412B2 (ja) * 2010-03-19 2014-11-12 国立大学法人京都大学 成形材料及びその製造方法
CN102407552B (zh) * 2011-10-21 2013-09-18 成都彩虹环保科技有限公司 多层纤维板成型装置
WO2013092817A1 (fr) * 2011-12-23 2013-06-27 Basf Se Matériaux lignocellulosiques comprenant des particules de matière plastique expansées réparties de façon non homogène dans le noyau
US20140004355A1 (en) * 2012-07-02 2014-01-02 Basf Se Multilayer lightweight woodbase materials composed of lignocellulosic materials having a core and two outer layers with treated pulp, treated natural fibers, synthetic fibers or mixtures thereof in the core
WO2015000913A1 (fr) * 2013-07-05 2015-01-08 Basf Se Substances à base de lignocellulose comportant des particules de matière plastique expansées munies d'un revêtement

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015052028A1 *

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Publication number Publication date
CN105612285A (zh) 2016-05-25
AR097985A1 (es) 2016-04-20
JP2016533918A (ja) 2016-11-04
AU2014334089A1 (en) 2016-04-21
PL3055453T3 (pl) 2024-04-29
WO2015052028A1 (fr) 2015-04-16
BR112016007573A2 (pt) 2017-08-01
KR20160068890A (ko) 2016-06-15
EP3055453B1 (fr) 2023-11-22
CL2016000831A1 (es) 2016-11-25
ES2973835T3 (es) 2024-06-24
EP3055453C0 (fr) 2023-11-22
US20160257814A1 (en) 2016-09-08
CA2926134A1 (fr) 2015-04-16

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